Wateepboofmg composition



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Arthur'- F. Taggnrt,

Serial No. 196,907

No Drawing. Application ch 19, 1938,

11 Claims.

. My invention relates to waterproofing compositions. and their methods of manufacture, and more particularly to waterproofing compositions that form, upon evaporation of their volatile con-- 5 'stituents; extremely fine-grained to class-like watenrepcllent films.

By the expression glass-like I refer to a substantially complete lack of visual evidence of structure and, without actual transparency, such N as characterlzm ordinary'window glass, on appearance of smoothness and continuity such as one observes in examining an oiled ground-glass surface with the naked eye. Similarly, in the eitpre'sslon "extremely fine-grained," the condi- Ifl tion described is one in which graininess is so nearly absent as to producebut a mere suggestion thereof in the mind of. an observer.

One of the features of myinvention is the crystallization oi a water-repellent crystalline no material in the composition from a medium in thickened form, whereby; the normal growth of the crystals is arrested and the material deposits in the form oi; extremely flne sine crystals.

; These extremely crystals uniformly and in- 25 tiznately admixwith the fine size particles of the substance causing the thickening to form upon complete solidification a, continuous extremely finegrained to-glass-like film the imperforate nature of which prevents moisture penetration.

Preliminarily to the discovery upon which my invention is baseuhl prepared and observed microscopically numerous slides of diflerent mixtitres of water-repellent, substances and" tested these mixtures for comparative waterproofing ef- 3,1 iectiveness. I observedirom these tests that the most effective waterprooflngmixtures, whatever the. ingredients used, were those that produced uniform and extremely flne arained to glass-like films. Such films, generally speaking, are com- 40 posed of ingredients that are so mely divided that no definite crystalline structure can be detected in the him when it is viewed through a microscope with dark field illumination and having a magnification of about 150 diameters.

Following these observations, I discovered that highly efllcient waterproofing compositions capable of producing the desired extremely finesrained to glass-like films may be consistently produced by admixing in the proper proportions 50 an organic solvent, a watch-repellent crystaliorzning material, and a substance that will cause the solvent and this substance to thicken sufficientiy before the crystoilizablematerial begins to crystallize, to arrest the growth of crystals 55 when the crystallizabl c material begins to solidify upon continued evaporation of the solvent. More specifically, I found that in order to effect the desired crystal growth control the concentration of the crystallizable material must be less than that at which the solvent would be super-- saturated with that material before the thickener and solvent has thickened.

An object of my invention is to provide a waterproofing composition containing an intimate admixture of various substances at least one of which is water-repellent, so related in solubility in the solvent used and in concentration therein, that whatever the substances used, the composi tion will form, upon evaporation of its volatile constituents, a highly water-repellent extremely fine-grained to glass-like film.

From the numerous microscopic observations that I have made of various waterproofing compositions, I have noticed that if the composition does not contain, at the time of crystallization of the crystallizable water-repellent material, a constituent that will interfere with the normal crystal growth of the crystallizable material, the latter will deposit in the form of relatively large, 11' regular and separated crystals. The films produced by such compositions are non-uniform and have a porphyritic or perforated structure that permits moisture penetration. These films are not satisfactory since they do not completely waterproof the materials to which they are applied. On the other hand, I have found that if the solvent and the constituents therein are properly chosen and their concentrations properly regulated to client the above mentioned crystal growthinterference, the compositions will produce upon solidification uniform, extremely finegrained to glass-like, imperforate, highly waterrepellent films.

In particular, I havediscovered that mineral waxes, such as parafiln, may be used as the waterrepellent crystallizable material. Heretofore it has been dimcult to produce efi'ective waterproof films comprising such waxes because they precipitate in large crystals yielding imperforate films. In accordance with my invention, mineral waxes, either alone or in admixture with other waterrepellent crystallizable materials, may be used to form eiiective waterproofing compositions.

I have also discovered, in particular, that asphalts and pitches of mineral origin may be used as the thickening ingredient for controlling the crystallization of the water-repellent crystallizable material, and that such asphalts and pitches may be used in coniunction with water repellent crystallizable materials of mineral origin, such as paraflin, as well as with crystallizable materials of organic origin, such as solid fats and waxes.

The rule or formula to be followed for producing the improved waterproofing compositions of my invention comprises selecting an organic solvent, a crystallizable water-repellent material, and a normally solid or viscous substance (preferably water-repellent) that is chemically or physically so related that the mixture of this substance and the solvent will thicken upon concentration thereof; and to so proportion them that the thickening will occur before the crystallizable water-repellent constituent or constituents in the liquid waterproofing composition begin to crystallize. In other words, when the waterproofing composition is applied to a material to be waterproofed and the organic solvent begins to evaporate, one of the constituents must first cause this substance and the solvent to thicken, either in the form of a gel or a viscous mass, so that when the crystallizable water-repellent material subsequently begins to precipitate out of solution the thickener and solvent will be in thickened form to interfere with the normal crystal growth of the precipitate so that the crystals of water-repellent material will be deposited in extremely fine size form, conducive to uniform intimate admixture with the normally fine size or amorphous particles of the thickener to produce upon the material to'be waterproofed a composite extremely fine-grained to glass-like water-repellent film.

One of the important and commercially valuable features of my invention is that the waterproofing composition may be made from any two or more materials, one of which is water-repellent, and a suitable solvent properly selected from large groups of such materials subsequently denoted herein and, in general, the same degree of waterproofing effectiveness will be obtained in each case. Regardless of the materials so selected, their maximum waterproofing efiective- "nem will always be produced so long as the crystallization of the crystallizable water-repellent material is properly controlled to produce very fine size crystals and thereby fine-grained films. As a result, the field of effective waterproofing compositions has been markedly extended.

While the exact water resistance of compositions produced from various mixtures of the selected water-repellent substances will vary somewhat inherently, they will each possess a high degree of water-repellence because of the finegrained, uniform, compact structure of their deposited films. That is to say, these films are composed of extremely small particles so uniform in size, admixture and distribution that the film is practically homogeneous and substantially 'rree of interstices. Consequently, the film offers a uniform high resistance to water over its entire surface and being practically non-porous it is impervious to water penetration.

In view of the fact that the only essential requirement for producing the desired type of waterproofing composition is proper selection of a substance that with the solvent will thicken sufilcien-tly at the proper concentrations to control the crystal growth of the water-repellent crystallizable material, it will be apparent that wide variations may be-made in the several constituentsused in the waterproofing composition as illustrated by the following.

The crystallizable water-repellent material, which constitutes one of the principal waterproofing ingredients in my composition, may be any water-repellent material that will crystallize upon concentration in an organic solvent. In a preferred modification I use a material of mineral origin. Examples are:

Hydrocarbons; e. g., paramn, ozokerite, montan, ceresin, and-others which are substantially solid at normal atmospheric temperatures,

Other water-repellent crystallizable substances that I have found satisfactory are as follows:

Fatty materials; e. g., both those natural fats and the artificially saturated animal, vegetable and marine fats and oils which crystallize and are substantially solid at normal atmospheric temperatures; such as lard, tallow, cocoa butter, fish and whale fats, hydrogenated animal oil, cotton seed, corn, cocoanut, peanut, fish and whale oils.

.Fatty acid glycerides; e. g., both those natural glycerides and those artificially saturated glycerides of the higher fatty acids found in animal, vegetable and marine fats which crystallize and are substantially solid at normal atmospheric temperatures, e. g., hydrogenated fish oil glycerides.

Higher fatty acids; e. g2, both those natural acids and those artificially saturated fatty acids found in animal, vegetable and marine fats, which crystallize and are substantially solid at normal atmospheric temperatures, e. g., stearic acid, hydrogenated fish oil acids.

Natural and artificial waxes; e. g., carnauba, wool wax, bees wax.

Higher alcohols and ketones; e. g., cetyl, ceryl, melissyl alcohols, and others which are substantially solid at normal atmospheric temperatures,

e. g., cholesterol and camphor.

These materials may be used alone or in admixture to form the water-repellent crystallizable ingredient of my composition.

' The solvent used may be any one of the organic evaporative solvents that will act as a common solvent for the thickener and the crystallizable material; and with the thickener will thicken upon evaporation of the solvent before the concentration of the crystallizable substance in the mixture becomes high enough for the precipitation of the crystallizable substance to start. Examples of solvents that I have found satisfactory are as follows:

1. Petroleum distillates of relatively high saturation in the gasoline-kerosene boiling range; e. g., petroleum naphtha, paraffin oil (kerosene).

2. Light aromatic hydrocarbons and substituted derivatives; e. 'g., benzol, toluol, xylol, nitrobenzene.

3. Oils derived by steam distillation of resinous woods; e. g., turpentine.

4. Halogene derivatives 0" lower hydrocarbons; e. g., carbon tetrachloride, chloroform, ethylene-dichloride.

5. Cellosolve.

The thickener may be any organic, preferably waterproof, substance that with the solvent will thicken at the proper concentration to control the crystal growth of the crystallizable waterrepellent materiaL- I have found it advantageous to use water-repellent substances as thickeners. These substances are of the type normally considered as amorphous, although X-ray analyses might show some or all of these subproper concentration and time to effect the desired crystal growth control. The thickener may be either of a gel-forming type or of a nongel-forming type. As far as the physical character of the thickener is concerned, it is only necessary that it and the solvent will be sufficiently viscous to physically interfere with the normal crystal growth of the crystallizable water-repellent material.

Examples of thickeners that I have found satisfactory for use in my invention are the following:

Asphaltic substances and pitches of mineral origin; e. g., natural and artificial asphalt, and earth and coal tar pitch.

I may also use: I

Metallic soaps; e. g., aluminum, copper zinc, calcium and iron stearates, oleates, palmitates, and the like.

Gum and resins; e. g., both the natural products such as rosin, copal, colophony, dammar,

' and the artificial neutral products such as the cumars.

Hydrocarbons; e. e., rubber.

Cellulosic materials; e. g., collodion (tetranitrate of cellulose), and Duco household cement."

When the thickener used in the waterproofing composition forms a gel or gel-like mass initially in the solvent, i. e., before concentration in the solvent, I have found it desirable to use a thinner or dispersing agent to disperse the gel and produce a mobile colloidal solution. This initial breaking or dispersing of the gel will not, however, if the proper dispersing agent is used, prevent the desired formation of gel or viscous mass for crystal growth control during eyaporation of the solvent when the composition is used. The thinner used for dispersing the initial gel should be a substance that volatilizes on evaporation of the mixture. Examples of the thinners or dispersing agents that I have found satisfactory are the following: Methyl, ethyl, butyl and amyl alcohols, phenol, cresol, aniline, toluidine, acetone and acetic acid.

Examples of various waterproofing compositions illustrating the proportions of ingredients necessary for crystal growth control and the formation of fine-grain films are as follows:

Example I Percent Percent Aluminum stearate (thickener) 2.0 3.0 Hydrogenated fish oil glycerides (crystalliza'ole l a O 9015 91315 0.5 0.5

Example II I Per cent Cumar (thickener) 80.00 Paraflin (crystallizable material) 0.75 Hydrogenated naphtha (solvent) 19.25

100.00 Example III Grams Asphalt (thickener) 20-25 Hydrogenated fish oil glycerides) (crystallizable material) 3 Hydrogenated fish oil acids (crystallizable material) 3 Hydrogenated naphtha (solvent) 100 Collodion solution consisting of tetra-nitrate of cellulose, ethyl alcohol and ethyl ether (thickener) c.c

Hydrogenated fish oil acids (crystallizable material) 0.3 Hydrogenated naphtha (solvent) 88.0 Ethyl alcohol (thinner) 1 Example IX Grams Asphalt (thickener) 2'0-25 Parafiin (orystallizable material) 2.7 Hydrogenated naphtha (solvent) 100 Example X i Percent Aluminum stearate (thickener) 3 Paraflin (crystallizable material) 3 Asphalt (thickenerf. 20-25 Ethyl alcohol (thinner) i 1 Hydrogenated naphtha (solvent) 73-68 Example XI Per cent Asphalt (thickener) 20-25 Paraflin (crystallizable material) 1 Hydrogenated fish oil (crystallizabie material) 1 Hydrogenated naphtha (solvent) '78-'73 Example XII Per cent Aluminum stearate (thickener) 3 Paraffin (crystallizable material) 1 Hydrogenated fish oil (crystallizable material)- 1 Ethyl alcohol (thinner) l Hydrogenated n'aptha (solvent) 94 It is to be understood that the above examples are not to limit the scope of my invention and that various other compositions may be pre- Example IV Per cent Aluminum stearate (thickener) 1.85 Hydrogenated fish oil glycerides (crystallizable material) 1.00 Carbon. tetrachloride (solvent) 96.15 Ethyl alcohol (thinner) 1.00

Example V Duco cellulosic cement (thickener) c. c 15 Hydrogenated fish oilglycerides (crystallizable material) --grams 0.1 Acetone (solvent) c.c 5 Hydrogenated naphtha (solvent) c.c 5

Example VI .Collodion solution consisting of tetranitrate of cellulose, ethyl alcohol and ethyl ether (thickener) c.c 5 Cholesterol (crystallizable material) l grams 0.025 v Example VII pared utilizing some of the other solvents, thickeners, crystallizable water-repellent materials, and thinners or dispersing agents listed hereinabove, and various combinations of these and 6 like materials having the necessary characteristics above describedfor producing the extremely fine-grained to glass-like films characteristic of my invention. 3

The tests that I have found satisfactory to 10 determine suitable solvents and thickeners (that is, those capable of producing upon concentration a marked increase in viscosity sufiicient to interfere with the normal crystal growth of the crystallizable water-repellent material and i5 proper proportions thereof) are as follows: A mixture is made of the thickener and the solvent that are desired to be used, and the mixture concentrated by evaporation to the point at which the mixture shows a marked increase in viscosity such as attended by gel formation or a definite tendency to string. If the mixture either gels or strings, the solvent and thickener are suitable. The concentration of' the solvent in the mixture when it reaches this point is then noted. Next, a mixture of a water-repellent orystallizable' material and solvent is made and evaporated'to the point at which precipitation of the crystallizable material begins. The concentration of solvent in the mixture at this point is noted.

Proportions of-crysta1lizable water-repellent material, thickener and solvent should now be chosen such that at the concentration at which the previous experiment has indicated that the thickener will produce definite stringing or gelling on evaporation of the.solvent, there shall be present in the mixture a quantity of solvent more than sufllcient to keep the crystallizable ingredient in solution.

The above tests may be checked by microscopic examination, such as the following: A drop of the waterproofing composition containing the solvent, the thickener, and the waterrepellent crystallizable material is placed on a 4g slide and examined after solidification under a microscope with dark field illumination and a magnification of about 150 diameters. If under these conditions the film appears fine-grained or glass-like, it is a satisfactory waterproofing film, indicating that the crystal growth of the crystallizable water-repellent material has been properly controlled by the thickener.

However, if definite crystals are scattered in porphyritic fashion throughout the mass of the film, the proportion of crystallizable material in the mixture is too high. A new mixture with slightly smaller proportion of crystallizable mate rial should then be tried until a satisfactory film is obtained. Alternatively, the same efiect can so be produced in some instances by adding to the,

composition a certain proportion of another mis= cible solvent in which the crystallizable mate= rial is more soluble and the thickener not more soluble. For example, when using the "Duco" 65 cement as the thickener with acetone as the solvent, a proportion of 0.1 gram of hydrogenated fish oil glycerides to 5 c. c, of cement gave a porphyritic structure. By adding to the mixture l c. c. of hydrogenated naphtha, which is a good 70 solvent for the glycerides, the film prepared with the same proportion of glycerides and cement was non-porphyritic; in other words, amorphous appearing and glass-like.

, In all of thecompositions mentioned above, it

7 will be understood that the proper proportioning of the thickener and the crystallizable materials isessential. The actual amounts of thickener and crystallizable material may vary from any useful small amount up to the amounts just short of those that would normally form super-satu- 5 rated solutions, that is, amounts sufiicient to cause precipitation of the solids in the waterproofing composition before it is applied for use. In other words, the extremely fine-grained to glass-like films are produced by precipitation 1 from the solution, and any desired amounts of materials less than the amount that will not go into solution may be used. The actual amounts of thickener and 'crystallizable materials used will depend largely upon the thickness of the water- 15 proofing film that it is desired to produce and upon the degree of penetration required. The thickness of the film is proportional to the amounts of solid materials present in the composition. The penetrativeness of the composition 20 is inversely proportional to the concentration of solids therein, the greater the concentration of solids the smaller the penetrativeness of the composition and vice versa.

The waterproofing compositions of my inven- 25 tion may be applied according to any well known methods, such as brush, spray, and immersion processes.

The waterproofing compositions of my invention may be prepared by any suitable admixing 30 of the several constituents, once the proper proportions thereof have been determined in the manner described hereinabove. For example, the thickener and the crystallizable material may be r admixed in solid form and heated until at least one of the materials. liquefles and causes all of the solids to. mutually dissolve. The proper amount of solvent is then added to this mixture of the thickener and crystallizable material. If 40 the thickener used is of the gel forming type, a relatively small amount, such as for example 1% or less of the thinner or dispersing agent, is added to the mixture, either before or after the solvent is added, for the purpose of producing a 45 thin penetrative mobile type of solution suitable for brushing, spraying or dipping processes.

Another method of preparing the composition comprises dissolving simultaneously the thickener and crystallizable material in the solvent, 5 applying heat and agitation, if necessary, to efiect solution of the solids in'the solvent. Still another method of preparing the composition, when using as the thickener a gel-forming material, comprises heating the thickener and solvent mixture 55 until a gel is formed, then adding to the gel a relatively small amount of the dispersing agent to disperse the gel into a mobile colloidal solution,

and then dissolving in this solution the crystallizable material.

From these examples it will be apparent that various other methods of preparing the compositions may be used and my invention is intended to cover any and all of such methods,

- It is to be understood that the doctrine of equivalents applies with full force and effect to this application and the invention disclosed herein and that various modifications and changes may be made in the materials and methods used without departing from the scope of this invention. The appended claims are directed to some of the novel features of my invention.

A portion of the disclosure in this application is contained in a copending joint application of the applicant et. al., Serial No. 138,364, filed April 22, 1937, now Patent No. 2,180,971 issued November 21, 1939.

I claim:

1. A mobile,'liquid, penetrative waterproofing composition that forms upon solidification an ex tremely fine-grained to glass-like water-repellent film, said composition comprising a normally solid crystallizable hydrophobic material comprised at least partially of a. mineral wax as the primary waterproofing ingredient; a water-repellent thickener; and a common solvent therefor; said ingredients being mixed in such proportions that upon concentration of the composition said thickener and solvent will thicken before said hydrophobic material begins to precipitate, whereby the thickener will arrest the normal crystal growth of the hydrophobic material when it begins to precipitate and cause it to precipitate in the form of extremely fine size crystals.

2. A mobile, liquid, penetrative waterproofing composition that forms upon solidification an extremely fine-grained to glass-like water-repellent film, said composition comprising a mineral wax as the primary waterproofing ingredient, a waterrepellent thickener, and a common solvent therefor; said ingredients being mixed in such proportions that upon concentration of the composition said thickener and solvent will thicken before said wax begins to precipitate, whereby the thickener will arrest the normal crystal growth of the wax when it begins to precipitate and cause it to precipitate in the form of extremely fine size crystals.

, 3. A mobile, liquid, penetrative waterproofing composition that forms upon solidification an extremely fine-grained to glass-like water-repellent film, said composition comprising paraffin as the primary waterproofing ingredient, a water-repellent thickener and a common solvent therefor. said ingredients being mixed in such proportions that upon concentration of the composition said thickener and solvent will thicken before said paraifin begins to precipitate, whereby the thickener will arrest the normal crystal growth of the parafiln when it begins to precipitate and cause it to precipitate in the form of extremely fine size crystals.

4. A mobile, liquid, penetrative waterproofing composition that forms upon solidification an extremely fine-grained to glass-like water-repellent film, said composition comprising paraffin, artificial asphalt, and a light hydrocarbon solvent, mixed in such proportions that upon concentration of the composition said asphalt and solvent will thicken before said parafiin begins to precipitate, whereby the thickened asphalt will arrest the normal crystal growth of the paraffin when it begins to precipitam and cause it to precipitate in the form of extremely fine size crystale.

5. A mobile, liquid, penetrative waterproofing composition that forms upon solidification an extremely fine-grained to glass-like water-repellent film, said composition comprising a wax of mineral origin, asphalt, and a light hydrocarbon solvent, mixed in such proportions that upon concentration of the composition said asphalt and solvent will thicken before said paramn begins to precipitate, whereby the thickened asphalt will arrest the normal crystal growth of the paraflin when it begins to precipitate and cause it to precipitate in the form of extremely fine size crystam.

6. A mobile, liquid, penetrative waterproofing composition that forms upon solidification an extremely fine-grained to glass-like water-repellent film, said composition comprising a mineral wax, a water-repellent thickener of mineral origin, and a common solvent therefor, mixed in such proportions that upon concentration of the composition said thickener and solvent will thicken before said wax begins to precipitate, whereby said thickener will arrest the normal crystal growth of the wax when it begins to precipitate and cause it to precipitate in the form of extremely fine size crystals.

7. A mobile, liquid, penetrative waterproofing composition that forms upon solidification an extremely fine-grained to glass-like water-repellent film, said composition comprising a crystallizable material comprised of parafiin and a hydrogenated oil; a thickener comprised of asphalt and aluminum stearate; and a light hydrocarbon solvent; said ingredients being mixed in such proportions that upon concentration of the composition said thickener and solvent will thicken before said crystallizable material begins to precipitate, whereby the thickener will arrest the normal crystal growth of the crystallizable material'when it begins to precipitate and cause it to precipitate in the form of extremely fine size crystals.

8. A mobile, liquid, penetrative waterproofing composition that forms upon solidification an extremely fine-grained to glass-like water-repellent film, said composition comprising a crystallizable material comprised of a mineral wax and a solid fat; a thickener comprised of asphalt and a water-insoluble soap; and alight hydrocarbon solvent; said ingredients being mixed in such proportions that upon concentration of the come position said thickener and solvent will thicken before said crystallizable material begins to precipitate, whereby the thickener will arrest the normal crystal growth of the crystallizable material when it begins to precipitate and cause it to precipitate in the form of extremely fine size crystals.

9. A mobile, liquid, penetrative waterproofing composition that forms upon solidification an extremely fine-grained to glass-like water-repellent film, said composition comprising a crystallizable material comprised of a mineral wax and a solid fat; a thickener comprised of a water-repellent thickener of mineral origin and a water-insoluble metallic soap; and a common solvent therefor; said ingredients being mixed in such proportions that upon concentration of the composition said thickener and solvent will thicken before said crystallizable material begins to precipitate, whereby the thickener will arrest the normal crystal growth of the crystallizable material when it begins to precipitate and cause it to precipitate in the form of extremely fine size crystals.

10. A mobile, liquid, penetrative waterproofing composition that forms upon solidification an extremely fine-grained to glass-like water-repellent film, said composition comprising parafiln, aluminum stearate and a light hydrocarbon solvent, mixed in such proportions that upon concentration of the composition said aluminum stearate and solvent will thicken before said parafiin begins to precipitate, whereby the thickened aluminum stearate gel will arrest the normal crystal growth of the paraffin when it begins to precipitate and cause it to precipitate in the form of extremely fine size crystals.

11. A mobile, liquid, penetrative waterproofing composition that forms upon solidification an extremely fine-grained to glass-like water-repellent film, said composition comprising a mineral wax, arrest the normal crystal growth of the wax a water-insoluble metallic soap, and a common when it begins to precipitate and cause it to presoivent therefor, mixed in such proportions that cipitate in the form of extremely fine size crysupon concentration of the composition said soap tals.

5 and solvent will thicken before said wax begins ARTHUR F. TAGGART. 5

to precipitate, whereby the thickened soap gel will 

